DOI QR코드

DOI QR Code

Multicomponent assessment and ginsenoside conversions of Panax quinquefolium L. roots before and after steaming by HPLC-MSn

  • Huang, Xin (Jilin Ginseng Academy, Changchun University of Chinese Medicine) ;
  • Liu, Yan (Institute of Special Animal and Plant Sciences, Chinese Academy of Agricultural Sciences) ;
  • Zhang, Yong (Jilin Ginseng Academy, Changchun University of Chinese Medicine) ;
  • Li, Shuai-Ping (Jilin Ginseng Academy, Changchun University of Chinese Medicine) ;
  • Yue, Hao (Jilin Ginseng Academy, Changchun University of Chinese Medicine) ;
  • Chen, Chang-Bao (Jilin Ginseng Academy, Changchun University of Chinese Medicine) ;
  • Liu, Shu-Ying (Jilin Ginseng Academy, Changchun University of Chinese Medicine)
  • Received : 2017.03.23
  • Accepted : 2017.08.01
  • Published : 2019.01.15

Abstract

Background: The structural conversions in ginsenosides induced by steaming or heating or acidic condition could improve red ginseng bioactivities significantly. In this paper, the chemical transformations of red American ginseng from fresh Panax quinquefolium L. under steaming were investigated, and the possible mechanisms were discussed. Methods: A method with reversed-phase high-performance liquid chromatography coupled with linear ion trap mass spectrometry ($HPLC-MS^n$)-equipped electrospray ionization ion source was developed for structural analysis and quantitation of ginsenosides in dried and red American ginseng. Results: In total, 59 ginsenosides of protopanaxadiol, protopanaxatriol, oleanane, and ocotillol types were identified in American ginseng before and after steaming process by matching the molecular weight and/or comparing $MS^n$ fragmentation with that of standards and/or known published compounds, and some of them were determined to be disappeared or newly generated under different steaming time and temperature. The specific fragments of each aglycone-type ginsenosides were determined as well as aglycone hydrated and dehydrated ones. The mechanisms were deduced as hydrolysis, hydration, dehydration, and isomerization of neutral and acidic ginsenosides. Furthermore, the relative peak areas of detected compounds were calculated based on peak areas ratio. Conclusion: The multicomponent assessment of American ginseng was conducted by $HPLC-MS^n$. The result is expected to provide possibility for holistic evaluation of the processing procedures of red American ginseng and a scientific basis for the usage of American ginseng in prescription.

Keywords

References

  1. Yuan CS, Wang CZ, Wicks SM, Qi LW. Chemical and pharmacological studies of saponins with a focus on American ginseng. J Ginseng Res 2010;34:160-7. https://doi.org/10.5142/jgr.2010.34.3.160
  2. Kim DH. Chemical diversity of panax ginseng panax quinquifolium, and panax notoginseng. J Ginseng Res 2012;36:1-15. https://doi.org/10.5142/jgr.2012.36.1.1
  3. Qi LW, Wang CZ, Yuan CS. Isolation and analysis of ginseng: advances and challenges. Nat Prod Rep 2011;28:467-95. https://doi.org/10.1039/c0np00057d
  4. Qi LW, Wang CZ, Yuan CS. Ginsenosides from American ginseng: chemical and pharmacological diversity. Phytochemistry 2011;72:689-99. https://doi.org/10.1016/j.phytochem.2011.02.012
  5. Ko SK, Cho OS, Bae HM, Sohn UD, Im BO, Cho SH, Chung SH, Lee BY. Change of ginsenoside composition of various American ginseng roots. J Korean Soc Appl Biol Chem 2009;52:198-201. https://doi.org/10.3839/jksabc.2009.036
  6. Kim WY, Kim JM, Han SB, Lee SK, Kim ND, Park MK, Kim CK, Park JH. Steaming of ginseng at high temperature enhances biological activity. J Nat Prod 2000;63:1702-4. https://doi.org/10.1021/np990152b
  7. Nam KY. The comparative understanding between red ginseng and white ginseng, processed ginsengs (Panax ginseng C. A. Meyer). J Ginseng Res 2005;29:1-18. https://doi.org/10.5142/JGR.2005.29.1.001
  8. Xie YY, Luo D, Cheng YJ, Ma JF, Wang YM, Liang QL, Luo GA. Steaming-induced chemical transformations and holistic quality assessment of red ginseng derived from Panax ginseng by means of HPLC-ESI-MS/MSn-based multicomponent quantification fingerprint. J Agric Food Chem 2012;60:8213-24. https://doi.org/10.1021/jf301116x
  9. Wu W, Qin QJ, Guo YY, Sun JH, Liu SY. Studies on the chemical transformation of 20(S)-PPT-type ginsenosides Re, Rg2, and Rf by using RRLC-Q-TOF-MS. J Agric Food Chem 2012;60:10007-14. https://doi.org/10.1021/jf302638f
  10. Kim MH, Lee YC, Choi SY, Cho CW, Rho J, Lee KW. The changes of ginsenoside patterns in red ginseng processed by organic acid impregnation pretreatment. J Ginseng Res 2011;35:497-503. https://doi.org/10.5142/jgr.2011.35.4.497
  11. Liu Z, Xia J, Wang CZ, Zhang JQ, Ruan CC, Sun GZ, Yuan CS. Remarkable impact of acidic ginsenosides and organic acids on ginsenoside transformation from fresh ginseng to red ginseng. J Agric Food Chem 2016;64:5389-99. https://doi.org/10.1021/acs.jafc.6b00963
  12. Lee MR, Yun BS, Sung CK. Comparative study of white and steamed black Panax ginseng, P. quinquefolium, and P. notoginseng on cholinesterase inhibitory and antioxidative activity. J Ginseng Res 2012;36:93-101. https://doi.org/10.5142/jgr.2012.36.1.93
  13. Ren GX, Chen F. Degradation of ginsenosides in American ginseng (Panax quinquefolium) extracts during microwave and conventional heating. J Agric Food Chem 1999;47:1501-5. https://doi.org/10.1021/jf980678m
  14. Sun BS, Xu MY, Li Z, Wang YB, Sung CK. UPLC-Q-TOF-MS/MS analysis for steaming times-dependent profiling of steamed panax quinquefolius and its ginsenosides transformations induced by repetitious steaming. J Ginseng Res 2012;36:277-90. https://doi.org/10.5142/jgr.2012.36.3.277
  15. Zeng F, Wang XM, Yang M, Lu ZQ, Guo DA. Fingerprint analysis of different Panax herbal species by HPLC-UV method. J Chin Pharm Sci 2007;16:277-81.
  16. Zhang X, Ma X, Si B, Zhao Y. Simultaneous determination of five active hydrolysis ingredients from Panax quinquefolium L. by HPLC-ELSD. Biomed Chromatogr 2011;25:646-51. https://doi.org/10.1002/bmc.1495
  17. Wang J, Bai HL, Liu CM, Li L. Isolation and purification of ginsenosides from plant extract of Panax quinquefolium L. by high performance centrifugal partition chromatography coupled with ELSD. Chromatographia 2009;71:267-71. https://doi.org/10.1365/s10337-009-1443-y
  18. Sun XB, Chen P, Cook SL, Jackson GP, Harnly JM, Harrington PB. Classification of cultivation locations of Panax quinquefolius L. samples using high performance liquid chromatographyelectrospray ionization mass spectrometry and chemometric analysis. Anal Chem 2012;84:3628-34. https://doi.org/10.1021/ac2032832
  19. Steinmann D, Ganzera M. Recent advances on HPLC/MS in medicinal plant analysis. J Pharm Biomed Anal 2011;55:744-57. https://doi.org/10.1016/j.jpba.2010.11.015
  20. Li M, Hou XF, Zhang J, Wang SC, Fu Q, He LC. Applications of HPLC/MS in the analysis of traditional Chinese medicines. J Pharm Anal 2011;1:81-91. https://doi.org/10.1016/S2095-1779(11)70015-6
  21. Yang M, Sun J, Lu Z, Chen G, Guan S, Liu X, Jiang B, Ye M, Guo DA. Phytochemical analysis of traditional Chinese medicine using liquid chromatography coupled with mass spectrometry. J Chromatogr A 2009;1216:2045-62. https://doi.org/10.1016/j.chroma.2008.08.097
  22. Shi Y, Sun CJ, Zheng B, Gao B, Sun AM. Simultaneous determination of ten ginsenosides in American ginseng functional foods and ginseng raw plant materials by liquid chromatography tandem mass spectrometry. Food Anal Methods 2013;6:112-22. https://doi.org/10.1007/s12161-012-9406-6
  23. Yang WZ, Ye M, Qiao X, Liu CF, Miao WJ, Bo T, Tao HY, Guo DA. A strategy for efficient discovery of new natural compounds by integrating orthogonal column chromatography and liquid chromatography/mass spectrometry analysis: its application in Panax ginseng, Panax quinquefolium and Panax notoginseng to characterize 437 potential new ginsenosides. Anal Chim Acta 2012;739:56-66. https://doi.org/10.1016/j.aca.2012.06.017
  24. Qi LW, Wang HY, Zhang H, Wang CZ, Li P, Yuan CS. Diagnostic ion filtering to characterize ginseng saponins by rapid liquid chromatography with time-offlight mass spectrometry. J Chromatogr A 2012;1230:93-9. https://doi.org/10.1016/j.chroma.2012.01.079
  25. Wan JY, Liu P, Wang HY, Qi LW, Wang CZ, Li P, Yuan CS. Biotransformation and metabolic profile of American ginseng saponins with human intestinal microflora by liquid chromatography quadrupole time-of-flight mass spectrometry. J Chromatogr A 2013;1286:83-92. https://doi.org/10.1016/j.chroma.2013.02.053
  26. Park HW, In G, Kim JH, Cho BG, Han GH, Chang IM. Metabolomic approach for discrimination of processed ginseng genus (Panax ginseng and Panax quinquefolius) using UPLC-QTOF MS. J Ginseng Res 2014;38:59-65. https://doi.org/10.1016/j.jgr.2013.11.011
  27. Wu W, Sun L, Zhang Z, Guo YY, Liu SY. Profiling and multivariate statistical analysis of Panax ginseng based on ultra-high-performance liquid chromatography coupled with quadrupole-time-of-flight mass spectrometry. J Pharm Biomed Anal 2015;107:141-50. https://doi.org/10.1016/j.jpba.2014.12.030
  28. Domon B, Costello CE. A systematic nomenclature for carbohydrate fragmentations in FAB-MS/MS spectra of glycoconjugates. Glycoconj J 1988;5:397-409. https://doi.org/10.1007/BF01049915
  29. Liu S, Cui M, Liu Z, Song F. Structural analysis of saponins from medicinal herbs using electrospray ionization tandem mass spectrometry. J Am Soc Mass Spectrom 2004;15:133-41. https://doi.org/10.1016/j.jasms.2003.09.013

Cited by

  1. Chemical Differentiation and Quantitative Analysis of Different Types of Panax Genus Stem-Leaf Based on a UPLC-Q-Exactive Orbitrap/MS Combined with Multivariate Statistical Analysis Approach vol.2018, 2018, https://doi.org/10.1155/2018/9598672
  2. Inhibitory Effects of Ginsenoside Ro on the Growth of B16F10 Melanoma via Its Metabolites vol.24, pp.16, 2019, https://doi.org/10.3390/molecules24162985
  3. Comprehensive Lipidome and Metabolome Profiling Investigations of Panax quinquefolius and Application in Different Growing Regions Using Liquid Chromatography Coupled with Mass Spectrometry vol.69, pp.23, 2021, https://doi.org/10.1021/acs.jafc.1c02241
  4. Effect of pulsed vacuum drying on drying kinetics and quality of roots of Panax notoginseng (Burk.) F. H. Chen (Araliaceae) vol.39, pp.16, 2021, https://doi.org/10.1080/07373937.2020.1761827
  5. Hypoglycemic and Hypolipidemic Effects of Malonyl Ginsenosides from American Ginseng (Panax quinquefolius L.) on Type 2 Diabetic Mice vol.6, pp.49, 2019, https://doi.org/10.1021/acsomega.1c04656